CN103374352A - Composite material of fluorescence magnetism composite microsphere and oxidized graphene and preparation method thereof - Google Patents
Composite material of fluorescence magnetism composite microsphere and oxidized graphene and preparation method thereof Download PDFInfo
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- CN103374352A CN103374352A CN2012101121748A CN201210112174A CN103374352A CN 103374352 A CN103374352 A CN 103374352A CN 2012101121748 A CN2012101121748 A CN 2012101121748A CN 201210112174 A CN201210112174 A CN 201210112174A CN 103374352 A CN103374352 A CN 103374352A
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Abstract
The invention provides a composite material of fluorescence magnetism composite microsphere and oxidized graphene and a preparation method thereof. The composite material is composed of an oxidized graphene material and fluorescence magnetism composite microsphere loaded on the surface of the oxidized graphene material. The saturation magnetization of the composite material of the fluorescence magnetism composite microsphere and oxidized graphene is 10-50emu/g, the emission peak is 500-600nm and the grain size of the fluorescence magnetism composite microsphere is 50-1000nm. According to the invention, the preparation method comprises the following steps of: by taking the oxidized graphene material as a carrier, modifying the surface of the oxidized graphene material with a carboxyl group; then modifying the surface of the fluorescence magnetism composite microsphere with an amidogen group; forming acid amides between the carboxyl group modified on the surface of the oxidized graphene material and the amidogen group modified on the surface of the fluorescence magnetism composite microsphere by using a stem grafting method; grafting the fluorescence magnetism composite microsphere on the surface of the oxidized graphene material to obtain the composite material of fluorescence magnetism composite microsphere and oxidized graphene. The composite material of fluorescence magnetism composite microsphere and oxidized graphene has excellent magnetic property and fluorescence property, and is expected to have a wide application prospect in the biomedical field, environmental management field and the like.
Description
Technical field
What the present invention relates to is a kind of matrix material that is applied in the fields such as bio-medical field and environmental improvement, relates to specifically a kind of fluorescence magnetic complex microsphere and graphene oxide composite material, the invention still further relates to this composite manufacture method.
Background technology
In recent years graphene oxide and metal nanoparticle (gold, platinum etc.), the composite manufacture of magnetic nano-particle (nickel oxide, cobalt oxide, Z 250 etc.) with and in the applied research development in the fields such as material, chemistry, biomedicine rapidly.Magnetic/functionalized graphene oxide has a wide range of applications in various fields; such as having optical limiting property because of it; in the escape injury application in field of protection eyes and device, because it has superparamagnetism, the application in magnetic target drug-carrying field and nuclear magnetic resonance field etc.
Quantum dot claims again semiconductor nano (QDs), it is a kind of semiconductor nanoparticle that can accept exciting light, produce fluorescence, cause people's concern because having good spectral signature and photochemical stability, and can be applicable to the aspects such as cell imaging, immunofluorescence detection, living imaging.The composite manufacture of quantum dot and Graphene with and be with a wide range of applications in the field at solar cell, flexible optoelectronic material, sensor.
The fluorescence magnetic complex microsphere refers to a kind of matrix material with core/shell structure of forming with coated with silica fluorescence magnetic Nano composite granules.Coat silicon dioxide layer in fluorescence magnetic composite particles outside, improved particle stability in vivo, had wide application potential in fields such as bio-medical field and environmental improvements.
The preparation method of magnetic nano-particle and graphene oxide composite material generally has hydrothermal method, solvent-thermal method, local reduction way, chemical precipitation method, chemical crosslink technique, Graft Method etc.At present, the preparation that Graft Method is controlled with its reaction conditions, reproduction is applied to well magnetic nano-particle and graphene oxide composite material.This method be take at the graphene oxide of the polyacrylic water-based magnetic fluid of magnetic Nano ferriferrous oxide nano-particle finishing and finishing acid chloride groups as reactant, prepared magnetic Nano ferriferrous oxide nano-particle and graphene oxide composite material by Graft Method.Such as: Li etc. have synthesized magnetic ferroferric oxide nano-particles-graphene oxide composite material [Ying Li by Graft Method, Jia Chu, Jingyao Qi, Xin L etc. An easy and novel approach for the decoration of graphene oxide by Fe
3O
4Nanoparticles. Applied Surface Science., 2011,257:6059 – 6062].
The preparation method of quantum dot and graphene composite material generally has hydrothermal method, solvent-thermal method, electrochemical process, Graft Method etc.At present, Graft Method with its environmental friendliness, reaction conditions is controlled, reproduction good and be applied to the preparation of quantum dot and graphene composite material.This method is to coat Cys in quantum dot outside, with the acid chloride groups of graphene oxide, prepares quantum dot and graphene oxide composite material by the ammonia solution again.Such as: Chu etc. have synthesized cadmium telluride quantum dot-graphene oxide composite material [Jia Chu by Graft Method, Xin L, Ping Xu etc. Fluorescent features of CdTe nanorods grafted to graphene oxide through an amidation process.J.Mater.Chem., 2011,21:11283 – 11287].
At present, grapheme material has the advantages such as conductivity at room temperature is fastest, the capacity of heat transmission is the strongest, specific surface area is large, mechanical strength is maximum and is widely used in the fields such as the energy, material, biology, medical treatment, environment.
Summary of the invention
The object of the present invention is to provide a kind of have simultaneously good magnetic property and fluorescence property, fluorescence magnetic complex microsphere and the graphene oxide composite material that can use in fields such as bio-medical field and environmental improvements; The present invention also aims to provide the preparation method of a kind of fluorescence magnetic complex microsphere and graphene oxide composite material.
The object of the present invention is achieved like this:
1, fluorescence magnetic complex microsphere of the present invention and graphene oxide composite material are comprised of graphene oxide material and the fluorescence magnetic complex microsphere that loads on the graphene oxide material surface, and general structure is Fe
3O
4-CdL/GO, "-" is two kinds of bonding forces between the material in the formula, comprises physical force and chemical bonding force; " L " is any one among S, Se, the Te in the structural formula; "/" is two kinds of junction symbols between the material in the structural formula; The saturation magnetization of described fluorescence magnetic complex microsphere and graphene oxide composite material is 10 ~ 50emu/g, and emission peak is 500 ~ 600nm, and the particle diameter of described fluorescence magnetic complex microsphere is 50 ~ 1000nm.
2, the preparation method of fluorescence magnetic complex microsphere of the present invention and graphene oxide composite material is:
1), oleic acid (OA) clad nano Z 250 (Fe
3O
4) nanoparticle (structural formula is Fe
3O
4@OA) preparation:
Be that Ferric Chloride Hydrateds and the hydration iron protochloride of 4 grams is that 1 ~ 2:1 mixes in molar ratio with total mass; then join in 30 ml waters; stirring is dissolved Ferric Chloride Hydrated and hydration iron protochloride fully; under the nitrogen protection; under 20 ~ 140 degrees centigrade temperature; in solution, add rapidly 5 ~ 20 milliliters of ammoniacal liquor; solution slowly splashes into 1 ~ 10 milliliter of oleic acid after becoming black, and time for adding is 5 ~ 60 minutes, then reacts under 40 ~ 140 degrees centigrade temperature 10 ~ 60 minutes again; be down to subsequently room temperature; with the pH value to 3 of the hydrochloric acid conditioning solution of 0.5 mol/L ~ 7, the black solid product is through washing, and dehydrated alcohol is washed; magnetic field separation obtains nanoparticle Fe
3O
4@OA.
2), the preparation of the nanoparticle of Coated with Oleic Acid cadmic compound quantum dot (general structure is CdL@OA):
(1), the preparation of the nanoparticle of Coated with Oleic Acid cadmium telluride quantum dot (structural formula is CdTe@OA):
1., be that 5 sodium borohydrides that restrain or POTASSIUM BOROHYDRIDE and tellurium powder are that 0.2 ~ 4:1 mixes in molar ratio with total mass; then join in 50 ml waters; under the nitrogen protection, reaction 1 minute under 0 ~ 50 degree centigrade temperature ~ obtained sodium hydrogen telluride or the hydrogen telluride potassium solution of 0.01 ~ 1 mol/L in 24 hours.
2.; be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.001 ~ 1 mol/L is that 1 ~ 10000:1 is mixed into 300 milliliters solution by volume with concentration; with the pH value to 3 of the sodium hydrate regulator solution of 1 mol/L ~ 12; under the nitrogen protection; inject sodium hydrogen telluride or the hydrogen telluride potassium solution of 0.01 ~ 1 mol/L; the mol ratio of Cadmium chloride fine powder and sodium hydrogen telluride or hydrogen telluride potassium is 0.2 ~ 10:1; under 0 ~ 200 degree centigrade temperature; stirring reaction 1 minute ~ 72 hours; then splash into 1 ~ 20 milliliter of oleic acid; time for adding is 5 ~ 60 minutes; then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes; transfer to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdTe@OA.
(2), the preparation of the nanoparticle of Coated with Oleic Acid CdSe quantum dots (structural formula is CdSe@OA):
1., be that 2 S-WATs that restrain and selenium powder are that 0.05 ~ 0.5:1 mixes in molar ratio with total mass; then under nitrogen protection; join in 50 ml waters of 20 ~ 80 degree celsius temperature; under the nitrogen protection, reaction 1 minute under 0 ~ 120 degree centigrade temperature ~ obtained the sodium thiosulfate solution of 0.01 ~ 1 mol/L in 48 hours.
2.; be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.001 ~ 1 mol/L is that 1 ~ 10000:1 is mixed into 300 milliliters solution by volume with concentration; with the pH value to 3 of the sodium hydrate regulator solution of 1 mol/L ~ 12; under the nitrogen protection; inject the sodium thiosulfate solution of 0.01 ~ 1 mol/L; the mol ratio of Cadmium chloride fine powder and sodium thiosulfate is 0.2 ~ 10:1; under 0 ~ 200 degree centigrade temperature; then stirring reaction 1 minute ~ 72 hours splashes into 1 ~ 20 milliliter of oleic acid, and time for adding is 5 ~ 60 minutes; then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes; transfer to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdSe@OA.
(3), the preparation of the nanoparticle of Coated with Oleic Acid cadmiumsulfide quantum dot (structural formula is CdS@OA):
Under nitrogen protection; 50 milliliters the concentration that 0.1 ~ 1 milliliter Thiovanic acid is added drop-wise to 20 ~ 180 degree celsius temperature is in the Cadmium chloride fine powder aqueous solution of 0.001 ~ 1 mol/L; time for adding is 5 ~ 60 minutes; with the pH value to 3 of the sodium hydrate regulator solution of 0.1 mol/L ~ 12; then under nitrogen protection; inject the sodium sulfide solution of 0.01 ~ 1 mol/L; the mol ratio of Cadmium chloride fine powder and sodium sulphite is 0.2 ~ 10:1; under 0 ~ 200 degree centigrade temperature; then stirring reaction 1 minute ~ 72 hours splashes into 0.01 ~ 10 milliliter of oleic acid, and time for adding is 5 ~ 60 minutes; then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes; transfer to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdS@OA.
3), (general structure is Fe to the fluorescence magnetic Nano composite granules
3O
4-CdL@OA) preparation of toluene magnetic fluid:
With total mass be 1 the gram CdL@OA and Fe
3O
4@OA is that 1 ~ 5:1 mixes in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 0.5 ~ 5 hour obtains the Fe of 10 grams per liters
3O
4-CdL@OA toluene magnetic fluid.
4), (general structure is Fe to the fluorescence magnetic complex microsphere
3O
4-CdL@SiO
2) preparation:
Distilled water, Virahol and ammoniacal liquor by volume for 1:10:0.1 ~ 1 is mixed into the solution of 115 milliliters of cumulative volumes, are then added 5 milliliters Fe
3O
4The tetraethoxy of-CdL@OA toluene magnetic fluid and 10 milliliters, under 0 ~ 100 degree centigrade temperature, stirring reaction 1 minute ~ 72 hours transfers to room temperature subsequently, obtains Fe after separation, washing, vacuum-drying
3O
4-CdL@SiO
2
5), (general structure is Fe to the fluorescence magnetic complex microsphere of finishing amino
3O
4-CdL@SiO
2-NH
2) preparation:
Fe with 2 grams
3O
4-CdL@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the amino silicane coupling agent that wherein adds 1 ~ 10 milliliter; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.1 ~ 1:1 and 2 ~ 20 ml solns of dry toluene, time for adding is 5 ~ 60 minutes; then under 0 ~ 200 degree centigrade temperature; stirring reaction 1 minute ~ 72 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdL@SiO
2-NH
2
6), the preparation of the graphene oxide of finishing carboxyl (structural formula is GO-COOH):
Be that graphene oxide (GO), sodium hydroxide and the Potcrate of 10 grams are that 0.01 ~ 0.1:0.5 ~ 5:1 mixes in mass ratio with total mass, then join in 100 ml waters, stirring reaction is 1 minute ~ 72 hours under 0 ~ 100 degree centigrade temperature, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), (general structure is Fe for fluorescence magnetic complex microsphere and graphene oxide composite material
3O
4-CdL/GO) preparation:
Be 100 milligrams Fe with total mass
3O
4-CdL@SiO
2-NH
2With GO-COOH be that 1 ~ 10:1 mixes in mass ratio, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 5 ~ 50 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 1 minute ~ 72 hours under 0 ~ 200 degree centigrade temperature, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material after the vacuum-drying.
Note:
1, in said structure formula and the general structure, "@" in the mixture of core/shell structure (mixture comprises nanoparticle, Nano composite granules, complex microsphere, matrix material), the contact surface between shell material and the core substance; "-" is two kinds of bonding forces between the material, comprises physical force and chemical bonding force; "/" is two kinds of junction symbols between the material; " OA " is oleic acid; " GO " is graphene oxide.
2, " (structural formula is Fe to the fluorescence magnetic complex microsphere of finishing amino
3O
4-CdL@SiO
2-NH
2) " (structural formula is Fe for the fluorescence magnetic complex microsphere
3O
4-CdL@SiO
2) the upper amino group of surface connection.
3, " graphene oxide of finishing carboxyl (structural formula is GO-COOH) " connects upper carboxylic group for the graphene oxide surface.
4, described Fe
3O
4-CdL@SiO
2-NH
2Be Fe
3O
4-CdS@SiO
2-NH
2, Fe
3O
4-CdSe@SiO
2-NH
2, Fe
3O
4-CdTe@SiO
2-NH
2In any one.
5, described Fe
3O
4-CdL@SiO
2Be Fe
3O
4-CdS@SiO
2, Fe
3O
4-CdSe@SiO
2, Fe
3O
4-CdTe@SiO
2In any one.
6, described Fe
3O
4-CdL@OA toluene magnetic fluid is Fe
3O
4-CdS@OA toluene magnetic fluid, Fe
3O
4-CdSe@OA toluene magnetic fluid, Fe
3O
4In-CdTe@OA toluene the magnetic fluid any one.
7, described Fe
3O
4-CdL@OA is Fe
3O
4-CdS@OA, Fe
3O
4-CdSe@OA, Fe
3O
4Among-CdTe@the OA any one.
8, described CdL@OA is any one among CdS@OA, CdSe@OA, the CdTe@OA.
9, described amino silicane coupling agent is any one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane.
10, described Fe
3O
4-CdL@SiO
2-NH
2With the mass ratio of GO-COOH be 1 ~ 10:1.
11, the mass ratio of described graphene oxide, sodium hydroxide and Potcrate is 0.01 ~ 0.1:0.5 ~ 5:1.
Compared with prior art, the present invention has following advantage:
The present invention is take the graphene oxide material as carrier, and at its finishing carboxylic group, then with fluorescence magnetic complex microsphere finishing amino group, adopt Graft Method to make between the amino group of the carboxylic group of graphene oxide finishing and the finishing of fluorescence magnetic complex microsphere and form acid amides, the fluorescence magnetic complex microsphere is grafted on the graphene oxide material surface obtains fluorescence magnetic complex microsphere and graphene oxide composite material, this fluorescence magnetic complex microsphere and graphene oxide composite material have good magnetic property and fluorescence property simultaneously, are expected to be with a wide range of applications in fields such as bio-medical field and environmental improvements.
Description of drawings
Fig. 1 is fluorescence magnetic complex microsphere and the graphene oxide composite material electronic transmission electromicroscopic photograph figure of embodiment 1.
Fig. 2 is the fluorescence magnetic complex microsphere electronic scanning electromicroscopic photograph figure of embodiment 1.
Fig. 3 is the test result comparison diagram of each embodiment.
Embodiment
Note: in each of the embodiments described below:
1, in structural formula, "@" in the mixture of core/shell structure (mixture comprises nanoparticle, Nano composite granules, complex microsphere, matrix material), the contact surface between shell material and the core substance; "-" is two kinds of bonding forces between the material, comprises physical force and chemical bonding force; "/" is two kinds of junction symbols between the material; " OA " is oleic acid; " GO " is graphene oxide.
2, " (structural formula is Fe to the fluorescence magnetic complex microsphere of finishing amino
3O
4-CdL@SiO
2-NH
2) " (structural formula is Fe for the fluorescence magnetic complex microsphere
3O
4-CdL@SiO
2) the upper amino group of surface connection.
3, " graphene oxide of finishing carboxyl (structural formula is GO-COOH) " connects upper carboxylic group for the graphene oxide surface.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA:
Be that Ferric Chloride Hydrateds and the hydration iron protochloride of 4 grams is 1.75:1 mixing in molar ratio with total mass; then join in 30 ml waters; stirring is dissolved Ferric Chloride Hydrated and hydration iron protochloride fully; under the nitrogen protection; under 40 degrees centigrade temperature; in solution, add rapidly 10 milliliters of ammoniacal liquor; solution slowly splashes into 2.5 milliliters of oleic acid after becoming black, and time for adding is 30 minutes, then reacts under 90 degrees centigrade temperature 30 minutes again; transfer to subsequently room temperature; with the pH value to 4 of the hydrochloric acid conditioning solution of 0.5 mol/L, the black solid product is through washing, and dehydrated alcohol is washed; magnetic field separation obtains nanoparticle Fe
3O
4@OA.
2), the preparation of the nanoparticle CdTe@OA of Coated with Oleic Acid cadmium telluride quantum dot:
1., be that sodium borohydrides and the tellurium powder of 5 grams mixes for 2:1 in molar ratio with total mass, then join in 50 ml waters, under the nitrogen protection, under 40 degrees centigrade temperature, react the sodium hydrogen telluride solution that obtained 0.48 mol/L in 1 hour.
2.; be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.012 mol/L is mixed into 300 milliliters solution by volume for 1000:1 with concentration; pH value to 9 with the sodium hydrate regulator solution of 1 mol/L; under the nitrogen protection; inject the sodium hydrogen telluride solution of 0.48 mol/L; the mol ratio of Cadmium chloride fine powder and sodium hydrogen telluride is 1:1; under 100 degrees centigrade temperature; then stirring reaction 2 hours splashes into 10 milliliters of oleic acid, and time for adding is 30 minutes; then under 100 degrees centigrade temperature, reacted again 30 minutes; be down to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdTe@OA.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdTe@OA toluene magnetic fluid:
With total mass be 1 the gram CdTe@OA and Fe
3O
4@OA mixes for 2:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdTe@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdTe@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:0.5, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdTe@OA toluene magnetic fluid and 10 milliliters, under 20 degrees centigrade temperature, stirring reaction 24 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdTe@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdTe@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdTe@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the γ-aminopropyl triethoxysilane that wherein adds 4 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 7 ml solns of dry toluene, time for adding is 30 minutes; then under 50 degrees centigrade temperature; stirring reaction 24 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdTe@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.02:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 24 hours under 20 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdTe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdTe@SiO
2-NH
2Mix for 2.5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 20 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 20 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdTe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdTe@OA of Coated with Oleic Acid cadmium telluride quantum dot: with embodiment 1.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdTe@OA toluene magnetic fluid: with embodiment 1.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdTe@SiO
2Preparation: with embodiment 1.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdTe@SiO
2-NH
2Preparation: with embodiment 1.
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.05:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 12 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdTe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdTe@SiO
2-NH
2Mix for 1:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 10 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 24 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdTe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdTe@OA of Coated with Oleic Acid cadmium telluride quantum dot: with embodiment 1.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdTe@OA toluene magnetic fluid: with embodiment 1.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdTe@SiO
2Preparation: with embodiment 1.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdTe@SiO
2-NH
2Preparation: with embodiment 1.
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.05:0.5:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 12 hours under 80 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdTe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdTe@SiO
2-NH
2Mix for 5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 40 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 24 hours under 100 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdTe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdTe@OA of Coated with Oleic Acid cadmium telluride quantum dot: with embodiment 1.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdTe@OA toluene magnetic fluid:
With total mass be 1 the gram CdTe@OA and Fe
3O
4@OA mixes for 1:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 0.5 hour obtains the Fe of 10 grams per liters
3O
4-CdTe@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdTe@SiO
2Preparation: with embodiment 1.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdTe@SiO
2-NH
2Preparation: with embodiment 1.
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.01:0.5:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 12 hours under 100 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdTe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdTe@SiO
2-NH
2Mix for 3:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 30 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 100 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdTe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdSe@OA of Coated with Oleic Acid CdSe quantum dots:
1., be that 2 S-WATs that restrain and selenium powder are that 0.1:1 mixes in molar ratio with total mass; then under nitrogen protection; join in 50 ml waters of 50 degree celsius temperature, under the nitrogen protection, reaction obtained the sodium thiosulfate solution of 0.03 mol/L in 36 hours under 100 degrees centigrade temperature.
2.; be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.001 mol/L is mixed into 300 milliliters solution by volume for 1000:1 with concentration; pH value to 9 with the sodium hydrate regulator solution of 1 mol/L; under the nitrogen protection; inject the sodium thiosulfate solution of 0.03 mol/L; the mol ratio of Cadmium chloride fine powder and sodium thiosulfate is 1:1; under 100 degrees centigrade temperature; then stirring reaction 36 hours splashes into 3 milliliters of oleic acid, and time for adding is 30 minutes; then under 100 degrees centigrade temperature, reacted again 60 minutes; transfer to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdSe@OA.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdSe@OA toluene magnetic fluid:
With total mass be 1 the gram CdSe@OA and Fe
3O
4@OA mixes for 2:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdSe@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdSe@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:0.5, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdSe@OA toluene magnetic fluid and 10 milliliters, under 20 degrees centigrade temperature, stirring reaction 24 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdSe@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdSe@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdSe@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the γ-aminopropyl triethoxysilane that wherein adds 4 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 7 ml solns of dry toluene, time for adding is 30 minutes; then under 50 degrees centigrade temperature; stirring reaction 24 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdSe@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.02:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 24 hours under 25 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdSe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdSe@SiO
2-NH
2Mix for 2.5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 20 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 20 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdSe/GO.Specific performance is seen Fig. 3.
Embodiment 6
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdSe@OA of Coated with Oleic Acid CdSe quantum dots: with embodiment 5.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdSe@OA toluene magnetic fluid: with embodiment 5.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdSe@SiO
2Preparation: with embodiment 5.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdSe@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdSe@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the N-β (aminoethyl)-γ-aminopropyl triethoxysilane that wherein adds 10 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 10 ml solns of dry toluene, time for adding is 60 minutes; then under 80 degrees centigrade temperature; stirring reaction 36 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdSe@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.05:0.5:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 36 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdSe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdSe@SiO
2-NH
2Mix for 1:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 10 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 36 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdSe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdSe@OA of Coated with Oleic Acid CdSe quantum dots: with embodiment 5.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdSe@OA toluene magnetic fluid: with embodiment 5.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdSe@SiO
2Preparation: with embodiment 5.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdSe@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdSe@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the γ-aminopropyltrimethoxysilane that wherein adds 2 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 5 ml solns of dry toluene, time for adding is 30 minutes; then under 100 degrees centigrade temperature; stirring reaction 12 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdSe@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.1:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 48 hours under 30 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdSe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdSe@SiO
2-NH
2Mix for 3:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 30 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 80 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdSe/GO.Specific performance is seen Fig. 3.
Embodiment 8
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdSe@OA of Coated with Oleic Acid CdSe quantum dots: with embodiment 5.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdSe@OA toluene magnetic fluid: with embodiment 5.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdSe@SiO
2Preparation: with embodiment 5.
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdSe@SiO
2-NH
2Preparation: with embodiment 5.
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.01:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 48 hours under 80 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdSe/GO:
Be 100 milligrams Fe with total mass
3O
4-CdSe@SiO
2-NH
2Mix for 5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 50 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 72 hours under 60 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdSe/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdS@OA of Coated with Oleic Acid cadmiumsulfide quantum dot:
Under nitrogen protection; 50 milliliters the concentration that 0.1 milliliter Thiovanic acid is added drop-wise to 50 degree celsius temperature is in the Cadmium chloride fine powder aqueous solution of 0.001 mol/L; time for adding is 30 minutes; pH value to 9 with the sodium hydrate regulator solution of 0.1 mol/L; then under nitrogen protection; inject the sodium sulfide solution of 0.06 mol/L; the mol ratio of Cadmium chloride fine powder and sodium sulphite is 0.2 ~ 10:1; under 160 degrees centigrade temperature; then stirring reaction 36 hours splashes into 0.1 milliliter of oleic acid, and time for adding is 30 minutes; then under 160 degrees centigrade temperature, reacted again 60 minutes; transfer to subsequently room temperature, through washing, dehydrated alcohol is washed; centrifugation obtains nanoparticle CdS@OA.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdS@OA toluene magnetic fluid:
With total mass be 1 the gram CdS@OA and Fe
3O
4@OA mixes for 2:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdS@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdS@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:0.5, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdS@OA toluene magnetic fluid and 10 milliliters, under 20 degrees centigrade temperature, stirring reaction 24 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdS@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdS@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdS@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the γ-aminopropyl triethoxysilane that wherein adds 4 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 7 ml solns of dry toluene, time for adding is 30 minutes; then under 50 degrees centigrade temperature; stirring reaction 24 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdS@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.02:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 24 hours under 40 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdS/GO:
Be 100 milligrams Fe with total mass
3O
4-CdS@SiO
2-NH
2Mix for 2.5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 20 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 20 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdS/GO.Specific performance is seen Fig. 3
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdS@OA of Coated with Oleic Acid cadmiumsulfide quantum dot: with embodiment 9.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdS@OA toluene magnetic fluid:
With total mass be 1 the gram CdS@OA and Fe
3O
4@OA mixes for 1:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdS@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdS@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:1, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdS@OA toluene magnetic fluid and 10 milliliters, under 50 degrees centigrade temperature, stirring reaction 36 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdS@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdS@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdS@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the γ-aminopropyltrimethoxysilane that wherein adds 8 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 10 ml solns of dry toluene, time for adding is 60 minutes; then under 80 degrees centigrade temperature; stirring reaction 48 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdS@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.05:1:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 24 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdS/GO:
Be 100 milligrams Fe with total mass
3O
4-CdS@SiO
2-NH
2Mix for 5:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 50 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdS/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdS@OA of Coated with Oleic Acid cadmiumsulfide quantum dot: with embodiment 9.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdS@OA toluene magnetic fluid:
With total mass be 1 the gram CdS@OA and Fe
3O
4@OA mixes for 5:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdS@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdS@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:0.1, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdS@OA toluene magnetic fluid and 10 milliliters, under 80 degrees centigrade temperature, stirring reaction 48 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdS@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdS@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdS@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the N-β (aminoethyl)-γ-aminopropyltrimethoxysilane that wherein adds 10 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 10 ml solns of dry toluene, time for adding is 60 minutes; then under 100 degrees centigrade temperature; stirring reaction 72 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdS@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.05:0.5:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 48 hours under 80 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdS/GO:
Be 100 milligrams Fe with total mass
3O
4-CdS@SiO
2-NH
2Mix for 1:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 50 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 80 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdS/GO.Specific performance is seen Fig. 3.
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA: with embodiment 1.
2), the preparation of the nanoparticle CdS@OA of Coated with Oleic Acid cadmiumsulfide quantum dot: with embodiment 9.
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdS@OA toluene magnetic fluid:
With total mass be 1 the gram CdS@OA and Fe
3O
4@OA mixes for 2.5:1 in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 1 hour obtains the Fe of 10 grams per liters
3O
4-CdS@OA toluene magnetic fluid.
4), fluorescence magnetic complex microsphere Fe
3O
4-CdS@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor are mixed into the solution of 115 milliliters of cumulative volumes by volume for 1:10:0.2, then add 5 milliliters Fe
3O
4The tetraethoxy of-CdS@OA toluene magnetic fluid and 10 milliliters, under 50 degrees centigrade temperature, stirring reaction 48 hours obtains Fe after separation, washing, vacuum-drying
3O
4-CdS@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdS@SiO
2-NH
2Preparation:
Fe with 2 grams
3O
4-CdS@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the N-β (aminoethyl)-γ-aminopropyl triethoxysilane that wherein adds 6 milliliters; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.4:1 and 8 ml solns of dry toluene, time for adding is 40 minutes; then under 60 degrees centigrade temperature; stirring reaction 72 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdS@SiO
2-NH
2
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are 0.01:0.5:1 mixing in mass ratio with total mass, then join in 100 ml waters that stirring reaction is 48 hours under 50 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains GO-COOH after the vacuum-drying.
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdS/GO:
Be 100 milligrams Fe with total mass
3O
4-CdS@SiO
2-NH
2Mix for 3:1 in mass ratio with GO-COOH, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 30 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 48 hours under 100 degrees centigrade temperature, through washing, dehydrated alcohol is washed, and centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdS/GO.Specific performance is seen Fig. 3.
Claims (10)
1. a fluorescence magnetic complex microsphere and graphene oxide composite material is characterized in that: this matrix material is comprised of graphene oxide material and the fluorescence magnetic complex microsphere that loads on the graphene oxide material surface, and general structure is Fe
3O
4-CdL/GO, "-" is two kinds of bonding forces between the material in the formula, comprises physical force and chemical bonding force, and " L " is any one among S, Se, the Te in the formula, and "/" is two kinds of junction symbols between the material in the formula; The saturation magnetization of described fluorescence magnetic complex microsphere and graphene oxide composite material is 10 ~ 50emu/g, and emission peak is 500 ~ 600nm, and the particle diameter of described fluorescence magnetic complex microsphere is 50 ~ 1000nm.
2. the preparation method of a fluorescence magnetic complex microsphere and graphene oxide composite material, it is characterized in that: this preparation method's concrete steps are as follows:
1), the nanoparticle Fe of Coated with Oleic Acid nano ferriferrous oxide
3O
4The preparation of@OA:
Be that Ferric Chloride Hydrateds and the hydration iron protochloride of 4 grams is that 1 ~ 2:1 mixes in molar ratio with total mass; then join in 30 ml waters; stirring is dissolved Ferric Chloride Hydrated and hydration iron protochloride fully; under the nitrogen protection; under 20 ~ 140 degrees centigrade temperature; in solution, add rapidly 5 ~ 20 milliliters of ammoniacal liquor; solution slowly splashes into 1 ~ 10 milliliter of oleic acid after becoming black, and time for adding is 5 ~ 60 minutes, then reacts under 40 ~ 140 degrees centigrade temperature 10 ~ 60 minutes again; be down to subsequently room temperature; with the pH value to 3 of the hydrochloric acid conditioning solution of 0.5 mol/L ~ 7, the black solid product is through washing, and dehydrated alcohol is washed; magnetic field separation obtains nanoparticle Fe
3O
4@OA, " OA " is oleic acid in the formula, and " " is the contact surface between shell material and the core substance in the mixture of core/shell structure, and mixture comprises nanoparticle, Nano composite granules, complex microsphere, matrix material;
2), the preparation of the nanoparticle CdL@OA of Coated with Oleic Acid cadmic compound quantum dot:
(1), the preparation of the nanoparticle CdTe@OA of Coated with Oleic Acid cadmium telluride quantum dot:
1., be that 5 sodium borohydrides that restrain or POTASSIUM BOROHYDRIDE and tellurium powder are that 0.2 ~ 4:1 mixes in molar ratio with total mass, then join in 50 ml waters, under the nitrogen protection, reaction 1 minute under 0 ~ 50 degree centigrade temperature ~ obtained sodium hydrogen telluride or the hydrogen telluride potassium solution of 0.01 ~ 1 mol/L in 24 hours;
2., be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.001 ~ 1 mol/L is that 1 ~ 10000:1 is mixed into 300 milliliters solution by volume with concentration, with the pH value to 3 of the sodium hydrate regulator solution of 1 mol/L ~ 12, under the nitrogen protection, inject sodium hydrogen telluride or the hydrogen telluride potassium solution of 0.01 ~ 1 mol/L, the mol ratio of Cadmium chloride fine powder and sodium hydrogen telluride or hydrogen telluride potassium is 0.2 ~ 10:1, under 0 ~ 200 degree centigrade temperature, stirring reaction 1 minute ~ 72 hours, then splash into 1 ~ 20 milliliter of oleic acid, time for adding is 5 ~ 60 minutes, then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation obtains nanoparticle CdTe@OA;
(2), the preparation of the nanoparticle CdSe@OA of Coated with Oleic Acid CdSe quantum dots:
1., be that 2 S-WATs that restrain and selenium powder are that 0.05 ~ 0.5:1 mixes in molar ratio with total mass, then under nitrogen protection, join in 50 ml waters of 20 ~ 80 degree celsius temperature, under the nitrogen protection, reaction 1 minute under 0 ~ 120 degree centigrade temperature ~ obtained the sodium thiosulfate solution of 0.01 ~ 1 mol/L in 48 hours;
2., be that the Cadmium chloride fine powder aqueous solution and the Thiovanic acid of 0.001 ~ 1 mol/L is that 1 ~ 10000:1 is mixed into 300 milliliters solution by volume with concentration, with the pH value to 3 of the sodium hydrate regulator solution of 1 mol/L ~ 12, under the nitrogen protection, inject the sodium thiosulfate solution of 0.01 ~ 1 mol/L, the mol ratio of Cadmium chloride fine powder and sodium thiosulfate is 0.2 ~ 10:1, under 0 ~ 200 degree centigrade temperature, then stirring reaction 1 minute ~ 72 hours splashes into 1 ~ 20 milliliter of oleic acid, and time for adding is 5 ~ 60 minutes, then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation obtains nanoparticle CdSe@OA;
(3), the preparation of the nanoparticle CdS@OA of Coated with Oleic Acid cadmiumsulfide quantum dot:
Under nitrogen protection, 50 milliliters the concentration that 0.1 ~ 1 milliliter Thiovanic acid is added drop-wise to 20 ~ 180 degree celsius temperature is in the Cadmium chloride fine powder aqueous solution of 0.001 ~ 1 mol/L, time for adding is 5 ~ 60 minutes, with the pH value to 3 of the sodium hydrate regulator solution of 0.1 mol/L ~ 12, then under nitrogen protection, inject the sodium sulfide solution of 0.01 ~ 1 mol/L, the mol ratio of Cadmium chloride fine powder and sodium sulphite is 0.2 ~ 10:1, under 0 ~ 200 degree centigrade temperature, then stirring reaction 1 minute ~ 72 hours splashes into 0.01 ~ 10 milliliter of oleic acid, and time for adding is 5 ~ 60 minutes, then under 0 ~ 200 degree centigrade temperature, reacted again 10 ~ 60 minutes, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation obtains nanoparticle CdS@OA;
3), fluorescence magnetic Nano composite granules Fe
3O
4The preparation of-CdL@OA toluene magnetic fluid:
With total mass be 1 the gram CdL@OA and Fe
3O
4@OA is that 1 ~ 5:1 mixes in mass ratio, then joins in 100 milliliters of toluene, and ultra-sonic dispersion 0.5 ~ 5 hour obtains the Fe of 10 grams per liters
3O
4-CdL@OA toluene magnetic fluid;
4), fluorescence magnetic complex microsphere Fe
3O
4-CdL@SiO
2Preparation:
Distilled water, Virahol and ammoniacal liquor by volume for 1:10:0.1 ~ 1 is mixed into the solution of 115 milliliters of cumulative volumes, are then added 5 milliliters Fe
3O
4The tetraethoxy of-CdL@OA toluene magnetic fluid and 10 milliliters, under 0 ~ 100 degree centigrade temperature, stirring reaction 1 minute ~ 72 hours transfers to room temperature subsequently, obtains Fe after separation, washing, vacuum-drying
3O
4-CdL@SiO
2
5), the fluorescence magnetic complex microsphere Fe of finishing amino
3O
4-CdL@SiO
2-NH
2Preparation:
With 4) in obtain 2 the gram Fe
3O
4-CdL@SiO
2Ultra-sonic dispersion is in 55 milliliters dry toluene; to the amino silicane coupling agent that wherein adds 1 ~ 10 milliliter; under the nitrogen protection, slowly splash into triethylamine that volume ratio is 0.1 ~ 1:1 and 2 ~ 20 ml solns of dry toluene, time for adding is 5 ~ 60 minutes; then under 0 ~ 200 degree centigrade temperature; stirring reaction 1 minute ~ 72 hours, through washing, dehydrated alcohol is washed; centrifugation obtains Fe after the vacuum-drying
3O
4-CdL@SiO
2-NH
2" the fluorescence magnetic complex microsphere of finishing amino, general structure is Fe
3O
4-CdL@SiO
2-NH
2" be that fluorescence magnetic complex microsphere surface connects upper amino group;
6), the preparation of the graphene oxide GO-COOH of finishing carboxyl:
Be that graphene oxide, sodium hydroxide and the Potcrate of 10 grams are that 0.01 ~ 0.1:0.5 ~ 5:1 mixes in mass ratio with total mass, then join in 100 ml waters, stirring reaction is 1 minute ~ 72 hours under 0 ~ 100 degree centigrade temperature, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation, obtain GO-COOH after the vacuum-drying, " GO " is graphene oxide in the formula, " graphene oxide of finishing carboxyl, structural formula are GO-COOH " connects upper carboxylic group for the graphene oxide surface;
7), fluorescence magnetic complex microsphere and graphene oxide composite material Fe
3O
4The preparation of-CdL/GO:
Be 100 milligrams Fe with total mass
3O
4-CdL@SiO
2-NH
2With GO-COOH be that 1 ~ 10:1 mixes in mass ratio, then join in 100 ml waters, the 1-ethyl-3-(3-dimethylaminopropyl that adds again 5 ~ 50 milligrams) phosphinylidyne diimmonium salt hydrochlorate, stirring reaction is 1 minute ~ 72 hours under 0 ~ 200 degree centigrade temperature, transfer to subsequently room temperature, through washing, dehydrated alcohol is washed, centrifugation obtains fluorescence magnetic complex microsphere and graphene oxide composite material Fe after the vacuum-drying
3O
4-CdL/GO.
3. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material is characterized in that:
Described Fe
3O
4-CdL@SiO
2-NH
2Be Fe
3O
4-CdS@SiO
2-NH
2, Fe
3O
4-CdSe@SiO
2-NH
2, Fe
3O
4-CdTe@SiO
2-NH
2In any one.
4. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material is characterized in that: described Fe
3O
4-CdL@SiO
2Be Fe
3O
4-CdS@SiO
2, Fe
3O
4-CdSe@SiO
2, Fe
3O
4-CdTe@SiO
2In any one.
5. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material is characterized in that: described Fe
3O
4-CdL@OA toluene magnetic fluid is Fe
3O
4-CdS@OA toluene magnetic fluid, Fe
3O
4-CdSe@OA toluene magnetic fluid, Fe
3O
4In-CdTe@OA toluene the magnetic fluid any one.
6. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material is characterized in that: described Fe
3O
4-CdL@OA is Fe
3O
4-CdS@OA, Fe
3O
4-CdSe@OA, Fe
3O
4Among-CdTe@the OA any one.
7. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material, it is characterized in that: described CdL@OA is any one among CdS@OA, CdSe@OA, the CdTe@OA.
8. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material, it is characterized in that: described amino silicane coupling agent is any one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane.
9. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material is characterized in that: described Fe
3O
4-CdL@SiO
2-NH
2With the mass ratio of GO-COOH be 1 ~ 10:1.
10. the preparation method of a kind of fluorescence magnetic complex microsphere according to claim 2 and graphene oxide composite material, it is characterized in that: the mass ratio of described graphene oxide, sodium hydroxide and Potcrate is 0.01 ~ 0.1:0.5 ~ 5:1.
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